Substituted amino aryl acetonitriles



Patented Aug. 7, 1951 SUBSTITUTED AMINO ARYL ACETONITRILES LeslieSchenck; Westfield, N. J., assignor to General Aniline & FilmCorporation, New York, N. Y., a corporation of Delaware No Drawing.Application October 29, 1949, Serial No. 124,519-

4 Claims. (01. 260-465) This invention relates to new substituted amino:tryl acetonitriles and methods for producing hem; t In the past it hasbeen known to produce mor p-aminobenzoylacetonitrile and this hasusually been done by a process involving a Friedel- Crafts reaction. Theyields by this process have been quite low. Q s

It is an object of the present invention to produce certain substitutedamino aryl acetonitriles.

It is a further object of the present invention to produce certainsubstituted aminobenzoylacetonitriles by an improved process giving goodyields.

These and other objects of the present invention are attained by theproducts of the process which comprises reacting a carbethoxyamino arylchloride, substituted corresponding to the substitution of the productrequired, with ethylcyanoacetate and an enolizing agent and hydrolyzingthe product.

The new compounds have the following general formula:

in which R, is an aryl group such as phenyl or naphthyl, X is selectedfrom the group consisting of.alkyl, halogen, alkoxy, phenyl and phenoxy,and wherein the cyano aceto group is in the mor ppositions to the aminogroup.

The following examples serve to illustrate preferred embodiments of theinvention but substitutions and variations may be made within the scopeof the appended claims.

Example I 100 parts 2-chloro-4-carbethoxyaminobenzoic acid is added to200 parts thionyl chloride The mixture is refluxed until the evolutionof hydrogen chloride ceases and the volatile solvent is then removed invacuum. The residual acid chloride is dissolved in 340 parts benzene,and added during a period of one hour at a temperature below 5 C. to amixture of 440 parts acetone 106 parts ethylcyanoacetate and 49 parts95% sodium methylate.

After stirring several hours below 5 C. the solution is drowned in waterand the product precipitated from the aqueous layer by the addition ofacetic acid. The crude 2-chlor-4-carbethoxyaminobenzoylethylcyanoacetateis hydrolyzed by refluxing for hour with a slight excess of 10% sodiumhydroxide solution. Upon cooling, ;the2-ch1or-4-aminobenzoylacetonitrile is precipitated by slowly addingacetic acid. The product is a white crystalline material having amelting point of l69'170'C.

Example II 1 Following the method presented in Example I, 2,5 dimethoxy4 carbethoxyaminobenzoylchloride is reacted with ethylcyanoacetate andthe product is hydrolyzed with dilute alkali to give2,5-dimethoxy-4-aminobenzoylacetonitrile having a melting point of168-l'71 C.

Example III Following the method presented in Example I,3-carbethoxyamino-4-chlorobenzoyl chloride is reacted withethylcyanoacetate and the product hydrolyzed with dilute alkali to give3-amino-4- chlorobenzoylacetonitrile having a melting point of 143-144"C.

Example IV Following the method presented in Example I,2-carbethoxyamino-5-chlorobenzoylchloride is reacted withethylcyanoacetate and the product hydrolyzed with dilute alkali to give2-amino-5- chlorobenzoylacetonitrile having a melting point of -112 C.

Example V Following the method presented in Example I,3-carbethoxyamino-4-phenoxybenzoylchloride is reacted withethylcyanoacetate and the product hydrolyzed with dilute alkali to give4-phenoxy-3-aminobenzoylacetonitrile having a melting point of C.

Example VI Following the method presented in Example I,2-methyl-4-carbethoxyaminobenzoylchloride was reacted withethylcyanoacetate and the product hydrolyzed with dilute alkali to give2-methyl-4-aminobenzoylacetonitrile having a melting point of 154-160"C.

In the above examples, the acid chloride may be precipitated withpetroleum ether instead of removing the volatile solvent. Furthermore,it is not necessary to dissolve the acid chloride in a solvent and addslowly to the other reactants since it is possible to mix them together.The hydrolysis step may be accomplished at a temperature lower than thereflux temperature. Alkaline reactants other than sodium hydroxide maybe used for the hydrolysis. Other inert solvents may be substituted asmay other enolizing agents such as other sodium alcoholates as will beapparent to those skilled in the art.

In the case of 2-chloro-4-aminobenzoylacetonitrile the reaction may berepresented as follows:

Additional compounds which have been produced by this process include2-nitro-4-amino benzoylacetonitrile, 4-pheny1-3aminobenzoylacetonitrile, and 2-chlor-4-aminonaphthoy1acetonitrile. I

These compounds are useful as intermediates in preparing magenta colorformers for color film.

4 I claim: 1. New compositions having the formula:

NHzIll-COCH1CN in which R is an aryl group, X is selected from the groupconsisting of alkyl, halogen, alkoxy, phenyl and phenoxy, and whereinthe cyano aceto group is in a position selected from the groupconsisting of meta and para to the amino group.

2. 2-ch1oro-4-aminobenzoylacetonitrile.

3. 4-phenoxy-3-aminobenzoylacetonitr1le.

4. 2-methy1-4-aminobenzoylacetonitrile.

LESLIE M. SCHENCK.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,950,421 Wahl Mar. 13, 19342,392,167 Long et a1. Jan. 1, 1946 OTHER REFERENCES Dorsch et al., J.Am. Chem. Soc., vol. 54, pp.

Long et al., J. Am. Chem. 800., vol. 69, pp. 990-995 (1947).

1. NEW COMPOSITIONS HAVING THE FORMULA: